This year's show honors Nobel Peace Prize laureate Liu Xiaobo, the Chinese dissident writer and human rights activist who is currently imprisoned in his home country.
Performers at the concert will include pop legend Barry Manilow, jazz group Jamroquai, pop singer Robyn, British pop band Florence and the Machine, pop singer Colbie Caillat, pianist Herbie Hancock, and singer-songwriter Elvis Costello.
Washington won the 2010 Tony Award for his work in Fences and previously starred on Broadway in Julius Caesar. He won two Academy Awards, for Glory and Training Day.
Hathaway's stage credits include Twelfth Night and Carnival. She received an Oscar nomination for Rachel Getting Married and will be seen later this month in the film Love and Other Drugs. She will also host the November 20 edition of Saturday Night Live.